This application relates to a fire-retarded polycarbonate resin composition.
Because of their strength and clarity, polycarbonate resins have a great many significant commercial applications. Unfortunately, polycarbonate resins are inherently flammable and can drip hot molten material causing nearby materials to catch fire as well. Thus, in order to safely utilize polycarbonates in many applications it is necessary to include additives which retard the flammability of the material and/or which reduce dripping. The challenge is to identify additives which accomplish this purpose without compromising the desirable properties of strength and clarity, without introducing new problems (such as the potential environmental problems associated with halogenated additives) and without prohibitively increasing the price.
A variety of different materials have been described for use in producing fire-retarded and/or drip-resistant polycarbonates. Exemplary of these are the materials described in U.S. Pat. Nos. 3,971,756, 4,028,297, 4,110,299, 4,130,530, 4,303,575, 4,335,038, 4,552,911, 4,916,194, 5,218,027 and 5,508,323. Notwithstanding these varied disclosures, however, there remains room for improvement in the formulation of fire-retarded polycarbonate resin.
Among the additives which are widely used commercially in fire-retarded polycarbonate resin compositions are organic salts, particularly sulfonic acid salts. Particular examples of these salts are perfluoroalkane sulfonates, such as potassium perfluorobutane sulfonate (xe2x80x9cKPFBSxe2x80x9d, also known as xe2x80x9cRimar saltxe2x80x9d). and potassium diphenylsulfone sulfonate (xe2x80x9cKSSxe2x80x9d) yield haze free compositions when blended with polycarbonate resin. The use of perfluoroalkane sulfonates in polycarbonate resins is described in U.S. Pat. No. 3,775,367. However, the benefits which can be obtained using these materials alone are limited and indeed additional additives are generally included. The conventional means for enhancing the fire-retardant properties of these type of compositions while retaining transparency has been the addition of soluble organic halogen additives. For example, commercial grades of LEXAN polycarbonate resin (eg. 940A, 920A) contain a combination of KSS (0.3 phr) and a tetrabromobisphenol A/bisphenol A copolymer (0.5 phr, net 0.13 phr bromine content). Without the bromine, the 920A and 940A grades have inconsistent/unreliable performance in the UL94 VO 125 mil flammability test that these grades are designed to meet. However, the brominated additive is unsuitable for compositions which are required to meet xe2x80x9cECO-friendlyxe2x80x9d standards, since these standards prohibit the inclusion of bromine or chlorine.
It has now been found that improved fire-retarded properties can be imparted to polycarbonate resin composition by incorporating into the polycarbonate a fire-retardant component comprising a perfluoroalkane sulfonate, such as potassium perfluorobutane sulfonate, and a cyclic siloxane, such as octaphenylcyclotetrasiloxane. The fire-retardant component is suitably added at levels to form a polycarbonate composition in which the perfluoroalkane sulfonate is present in an amount of from 0.02 to 0.1 phr relative to the composition as a whole, and the cyclic siloxane is present in an amount of at least 0.02 relative to the composition as a whole.
The present invention relates to fire-retarded compositions comprising polycarbonate resin. The polycarbonate component of the compositions may be of any grade and made by any method. Thus, for example, the polycarbonate may be made via interfacial processes or by catalytic transesterification. The polycarbonate may be either branched or linear in structure, and may include functional substituents. Polycarbonate copolymers are also included within the invention. Techniques for manufacture of polycarbonates by these processes are well known, for example from U.S. Pat. Nos. 3,030,331, 3,169,121, 4,130,548, 4,286,083, 4,552,704, 5,210,268 and 5,606,007.
Once the polycarbonate resin is prepared, it is compounded with a fire-retardant component. In accordance with the invention, this fire retardant component comprises a perfluoroalkane sulfonate and a cyclic siloxane.
As noted above, perfluoroalkane sulfonates useful in the invention are described in U.S. Pat. No. 3,775,367. The most commonly employed of these materials is potassium perfluorobutane sulfonate which is commercially available from multiple sources. The perfluoroalkane sulfonate is included in the composition at a level sufficient to impart fire-retardant properties. In general, this will be in an amount of from 0.02 to 0.1 phr, based on the total weight of the composition. Amounts in excess of 0.1 phr may lead to haze in the compounded product, and do not lead to improved flame-retardant performance.
The cyclic siloxane is included in the composition at a level sufficient to impart improved fire-retardant properties in the presence of the perfluoroalkane sulfonate. In general, this will be in an amount of from 0.02 to 0.3 phr, based on the total weight of the composition. Suitable cyclic siloxanes which may be employed in the present invention include those with the general formula: 
wherein R is independently selected from the group consisting of C1 to C36 alkyl, fluorinated or perfluorinated C1 to C36 alkyl, C1 to C36 alkoxy, C6 to C14 aryl, aryloxy of 6 to 14 carbon atoms, arylalkoxy of 7 to 36 carbon atoms, and C1 to C36 alkyl-substituted aryl of 6 to 14 carbon atoms. Specific examples of cyclic siloxanes include, but are not limited to: octaphenylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, and tetramethyltetraphenylcyclotetrasiloxane.
The perfluoroalkane sulfonate and cyclic siloxane are blended with molten polycarbonate, for example in a screw-type extruder, and extruded and molded into parts of desired shapes. They may be added to the polycarbonate in combination, for example as a fire-retardant additive composition comprising a perfluoroalkane sulfonate and a cyclic siloxane, or sequentially in either order. A fire-retardant composition in accordance with the invention suitably comprises the perfluoroalkane sulfonate and the cyclic siloxane in a ratio of from about 0.07 to 5 by weight.
For purposes of testing fire-retardant properties, bars were molded from extruded polycarbonate containing potassium perfluorobutane sulfonate and cyclic siloxane in varying amounts. These compositions were found to exhibit a substantial improvement in fire-retardant properties, as reflected in the examples set forth below. Although the mechanism of action is not understood, this result appears to arise from a synergistic interaction of the fire-retardant ingredients, since a similar improvement was not observed for combinations of KSS and the cyclic siloxane. In addition, although the small scale experiments reported herein did not show this conclusively, larger scale runs showed that use of the fire-retardant composition of the invention resulted in polycarbonate with reduced haze.
The compositions of the invention may include conventional additives which are known in the art for inclusion in polycarbonate compositions. Such additives include but are not limited to stabilizers, mold release agents, light stabilizers, heat stabilizers, pigments and dyes.
The invention will now be further described by way of the following, non-limiting examples.